Metal–organic frameworks as selectivity regulators for hydrogenation reactions

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Abstract

Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon–oxygen group (in preference to the carbon–carbon group)1. However, developing effective catalysts for this transformation is challenging2,3,4,5,6,7, because hydrogenation of the carbon–carbon group is thermodynamically favoured8. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not9,10,11,12,13,14. This has inspired the use of metal–organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material15,16,17,18. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon–oxygen rather than the carbon–carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design strategy will allow the development of other selective heterogeneous catalysts for important yet challenging transformations.

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Figure 1: Sandwich MIL-101@Pt@MIL-101 nanostructures.
Figure 2: Investigation of the reaction mechanism on MIL-101@Pt.
Figure 3: XPS profiles of Pt, Fe, Cr and O in different catalysts.

Change history

  • 02 October 2016

    A footnote symbol was corrected in Table 1

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Acknowledgements

This work was supported financially by the National Research Fund for Fundamental Key Project (grant 2014CB931801 to Z.T.), the National Natural Science Foundation of China (grants 21475029 and 91427302 to Z.T., and 21303029 to G.L.), the Instrument Developing Project of the Chinese Academy of Sciences (grant YZ201311 to Z.T.), the CAS-CSIRO Cooperative Research Program (grant GJHZ1503 to Z.T.), the Strategic Priority Research Program of the Chinese Academy of Sciences (grant XDA09040100 to Z.T.), and the Youth Innovation Promotion Association CAS (grant 2016036 to G.L.). We gratefully acknowledge the use of the supercomputer facilities at the National Computational Infrastructure (NCI) in Canberra, Australia.

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Z.T. and G.L. proposed the research direction and guided the project. M.Z., K.Y. and G.L. designed and performed the materials synthesis, characterization, and catalytic tests. Y.W. and H.Z. performed the theoretical calculations and explained the catalytic results. J.G. helped to detect and analyse the Brunauer–Emmett–Teller (BET) surface areas and pore-size distributions of samples. L.G. guided the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging of sandwich structures. W.H. took part in the characterization of some samples, and discussed the results. Z.T., G.L., M.Z. and Y.W. drafted the manuscript. All of the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Guodong Li or Huijun Zhao or Zhiyong Tang.

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The authors declare no competing financial interests.

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Reviewer Information Nature thanks P. Claus and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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This file contains Supplementary Methods, Supplementary Text, Supplementary Notes 1-5, Supplementary Figures 1-54, Supplementary Tables 1-11 and Supplementary references. (PDF 14827 kb)

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Zhao, M., Yuan, K., Wang, Y. et al. Metal–organic frameworks as selectivity regulators for hydrogenation reactions. Nature 539, 76–80 (2016). https://doi.org/10.1038/nature19763

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